US7459106B2 - Materials, methods, and uses for photochemical generation of acids and/or radical species - Google Patents

Materials, methods, and uses for photochemical generation of acids and/or radical species Download PDF

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US7459106B2
US7459106B2 US10/473,365 US47336504A US7459106B2 US 7459106 B2 US7459106 B2 US 7459106B2 US 47336504 A US47336504 A US 47336504A US 7459106 B2 US7459106 B2 US 7459106B2
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Seth Marder
Joseph Perry
Wenhui Zhou
Stephen M. Kuebler
J. Kevin Cammack
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University of Arizona
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    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03CPHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00Photosensitive materials
    • G03C1/72Photosensitive compositions not covered by the groups G03C1/005 - G03C1/705
    • G03C1/73Photosensitive compositions not covered by the groups G03C1/005 - G03C1/705 containing organic compounds
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00Compounds containing amino groups bound to a carbon skeleton
    • C07C211/43Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C07C211/54Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to two or three six-membered aromatic rings
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C381/00Compounds containing carbon and sulfur and having functional groups not covered by groups C07C301/00 - C07C337/00
    • C07C381/12Sulfonium compounds
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D295/00Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/04Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms
    • C07D295/08Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly bound oxygen or sulfur atoms
    • C07D295/096Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly bound oxygen or sulfur atoms with the ring nitrogen atoms and the oxygen or sulfur atoms separated by carbocyclic rings or by carbon chains interrupted by carbocyclic rings
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D295/00Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/04Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms
    • C07D295/12Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly or doubly bound nitrogen atoms
    • C07D295/135Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly or doubly bound nitrogen atoms with the ring nitrogen atoms and the substituent nitrogen atoms separated by carbocyclic rings or by carbon chains interrupted by carbocyclic rings
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004Photosensitive materials
    • G03F7/0045Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004Photosensitive materials
    • G03F7/038Macromolecular compounds which are rendered insoluble or differentially wettable
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20Exposure; Apparatus therefor
    • G03F7/2051Exposure without an original mask, e.g. using a programmed deflection of a point source, by scanning, by drawing with a light beam, using an addressed light or corpuscular source
    • G03F7/2053Exposure without an original mask, e.g. using a programmed deflection of a point source, by scanning, by drawing with a light beam, using an addressed light or corpuscular source using a laser

Definitions

  • the invention relates to compositions and compounds that have large two-photon or higher-order absorptivities, which, after excitation, generate Lewis or Br ⁇ nsted acids, radicals or a combination thereof
  • the invention also relates to methods of making and using the compositions and compounds.
  • Two-photon or higher-order absorption refers to the initial simultaneous absorption of two or more photons (also referred to as multi-photon absorption) without the actual population of an excited state by the absorption of a single photon.
  • the exciting light is not attenuated by single-photon absorption in this case, it is possible to excite selectively molecules at a greater depth within a material than would be possible via single-photon excitation by use of a beam that is focused to that depth in the material.
  • These two advantages also apply to, for example, excitation within tissue or other biological materials.
  • the nonlinear scaling of absorption with intensity can lead to the ability to write features of a size below the diffraction limit of light, and the ability to write features in three dimensions, which is also of interest for holography.
  • molecules from the aforementioned classes can be excited efficiently by simultaneous two-photon (or higher-order) absorption, leading to efficient generation of electronically excited states.
  • These excited state species can be exploited in a great variety of chemical and physical processes, with the advantages enabled by multiphoton excitation.
  • polymerizable resin formulations containing cross-linkable acrylate containing monomers and D- ⁇ -D molecules as two-photon initiators of radical polymerization
  • complex three-dimensional objects can be prepared using patterned two-photon excitation.
  • Most two-photon induced photopolymerization processes involve radical reactions in which there is some volume decrease upon polymerization (Cumpston et al. Nature 398, (1999) 51; Belfield, K. D. et al. J. Am. Chem. Soc. 122, (2000) 1217).
  • expoxide monomers as well as others, such as vinyl ether monomers, can be photo-polymerized under one photon excitation conditions using iodonium salts and sulfonium salts as photoacid generating initiators as described by: Crivello, J. V.; Lam, J. H. W. Macromolecules, 1977, 10, 1307; DeVoe, R. J.; Sahyn, M. R. V.; Schmidt, E. Can. J. Chem. 1988, 66, 319; Crivello, J. V.; Lee, J. J. Polym. Sci. Polym. Chem.
  • dialkyl aryl sulfonium ions as described by Saeva, F. D.; Morgan, B. P. J. Am. Chem. Soc., 1984, 106, 4121; Saeva, F. D. Advances in Electron Transfer Chem. 1994, 4, 1, which are incorporated herein by reference—and iodonium salts can be sensitized through electron transfer by the addition of other molecules.
  • iodonium salts include Class I and Class II photoacid generating species, as described by Saeva et al. (cited above).
  • One object of the invention is to provide compounds and compositions which can be efficiently photoactivated by two- or multi-photon excitation to yield acid and/or radical species and which consequently overcome the limitations associated with conventional compounds and compositions.
  • Another embodiment of the present invention provides a method for making an article, which includes contacting the above compound or composition with at least one polymerizable or cross-linkable monomer, oligomer, or prepolymer, or acid-modifiable medium (such as ester-functionalized chemically amplified resins);
  • Another embodiment of the present invention provides an article, produced by the above process.
  • Another embodiment of the present invention provides a method for generating a Br ⁇ nsted or Lewis acid and/or radical, which includes irradiating the above compound or composition to cause a simultaneous two-photon or multiphoton absorption in the chomophore.
  • Another embodiment of the present invention provides a compound or composition, which includes:
  • Another embodiment of the present invention provides an apparatus, which includes:
  • FIG. 1 Two-photon dye covalently attached to a photoacid.
  • FIG. 2 Two-photon dye non-covalently attached to a photoacid.
  • FIG. 3 Photopolymerization kinetics of cyclohexene oxide initiated by different triphenylamine sulfonium salts in dichloromethane irradiated at 300 nm. Concentration of monomer: 7.91 mol/L; concentration of initiator: 3.16 ⁇ 10 ⁇ 3 mol/L. Lines are a guide to the eye.
  • FIG. 4 Photopolymerization initiated by different initiators in CH 2 Cl 2 at 419 nm [monomer]: 7.906 mol/L; [initiator]: 7.906 ⁇ 10 ⁇ 3 mol/L.
  • FIG. 5 Conversion of epoxy acrylate CN-115 initiated by 87 monitored by IR at 810 cm ⁇ 1 .
  • Resin MeCN, 20% w.t. of CN115; 87, 2% w.t. of CN115.
  • FIG. 6 a Conversion of epoxy acrylate CN-115 initiated by different piperazine stilbene systems monitored by IR Solvent: Tetrahydrofuran 20% w.t. of CN115.
  • FIG. 6 b Conversion of epoxy acrylate CN-115 initiated by different piperazine bistyrylbenzene systems monitored by IR Solvent: Tetrahydrofuran 20% w.t. of CN115.
  • the inset is a plot of log [H + ] against log [excitation power/mW] at 745 nm.
  • the smooth curve is the best fit of a line to the data and has a slope of 2.3.
  • FIG. 8 Structures of some conventional PAGs.
  • CD1012 [4-[(2-hydroxytetradecyl)oxy]phenyl]phenyliodonium hexafluoroantimonate (Sartomer)
  • ITX isopropylthioxanthone
  • TPS triphenylsulfonium hexafluoroantimonate.
  • FIG. 9 Images of microstructures created by patterned two-photon irradiation of an epoxide resin containing the compound 41.
  • (a) Scanning electron micrograph (SEM) of microstructures created with average exposure powers of 1-5 mW.
  • SEM Scanning electron micrograph
  • FIG. 10 Scanning electron micrograph of free-standing columnar features formed by two-photon-induced polymerization of a liquid epoxide resin containing 41.
  • compounds preferably derived from TPA dyes such as D- ⁇ -D, D-A-D and A-D-A as described above, but in which the dye skeleton is finctionalized with a group capable of generating a Lewis or Br ⁇ nsted Acid and/or radical after excitation of the dye moiety, can generate reactive species, and preferably acids or radical species.
  • dyes containing either a sulfonium group or an iodonium group in a single molecule can be effective at generating Lewis or Br ⁇ nsted Acids (and/or radicals) under one, two, or higher order photon excitation. These acids or radicals can subsequently react with additional species in a beneficial manner.
  • these materials can be used beneficially as one or two-photon initiators for polymerization of expoxide containing monomers.
  • These compounds exhibit enhanced two-photon or multi-photon absorptivities and allow one to control the position of two-photon or multi-photon absorption bands.
  • bridge it is meant a molecular fragment that connects two or more chemical groups.
  • donor an atom or group of atoms with a low ionization potential that can be bonded to a ⁇ -conjugated bridge.
  • exemplary donors in order of increasing strength, are (where R denotes an alkyl, aryl, or alkoxy group as defined below, where X(O) indicates that the element oxygen is double bonded to the element X, and where * indicates the point of attachment to the ⁇ -conjugated bridge):
  • acceptor an atom or group of atoms with a high electron affinity that can be bonded to a ⁇ -conjugated bridge.
  • exemplary acceptors in order of increasing strength, are (where R denotes an alkyl, aryl, or alkoxy group as defined below, where X(O) indicates that the element oxygen is double bonded to the element X, and where * indicates the point of attachment to the ⁇ -conjugated bridge):
  • aromatic group it is meant a carbocyclic group that contains 4n+2 ⁇ -electrons where n is an integer (and which may preferably have values of 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, and 24).
  • exemplary aryl groups include phenyl, naphthyl anthracenyl, and pyrenyl.
  • heteroaromatic group a cyclic group of atoms, with at least one atom within the ring being an element other than carbon, that contains 4n+2 ⁇ -electrons where n is an integer (and which may preferably have values of 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, and 24).
  • exemplary heteroaromatic groups include furanyl, thiophenyl, pyrrolyl, selenophenyl and tellurophenyl.
  • chromophore it is meant a molecule or aggregate of molecules that can absorb electromagnetic radiation.
  • excited state it is meant an electronic state of a molecule wherein electrons populate an energy state that is higher than another energy state for the molecule.
  • two-photon absorption it is meant the process wherein a molecule is promoted to an excited state by the simultaneous absorption of two quanta of electromagnetic radiation.
  • multi-photon absorption it is meant a process wherein a molecule absorbs is promoted to an excited state by the simultaneous absorption of two or more quanta of electromagnetic radiation.
  • a “ ⁇ -conjugated bridge” contains covalent bonds between atoms that both have ⁇ -(sigma) and ⁇ -bonds formed between two atoms by overlap of their atomic orbitals (s+p hybrid atomic orbitals for ⁇ bonds; p atomic orbitals for r bonds) with two orbitals (sp 3 , sp 2 , sp) overlapping end-to-end to form a a bond lying directly between the nuclei.
  • a ⁇ -conjugated bridge is one having a formal structure that contains double or triple bonds alternating with single bonds where the double and triple bonds are capable of further ⁇ overlap with each other.
  • Such bridges are said to be ⁇ -conjugated and include conjugated double or triple bonds.
  • heterolytic cleavage it is meant the fragmentation of a two-electron chemical bond such that the two electrons that composed the bond both reside on one of the two fragments formed.
  • homolytic cleavage it is meant the fragmentation of a two-electron chemical bond such that each of the two fragments formed is formed with one of the two electrons that composed the bond.
  • a Br ⁇ nsted acid is a proton or a proton donor.
  • a Lewis acid is a species that is electron deficient and behaves as an electron acceptor.
  • a resin is a mixture of materials and/or compounds at least one of which is capable of undergoing a chemical reaction that can change the physical properties of the mixture. For example, it can render the mixture less soluble or more soluble in a solvent.
  • a radical is a species that possesses one or more unpaired electrons.
  • a binder is a material and/or compound, which is a component of a resin, and which can increase the viscosity of the resin to such a point that the resin can be conveniently cast into a film under suitable processing conditions.
  • Photochemical hardening is a process in which the viscosity of solubility of a material increases upon exposure to electro-magnetic radiation, preferably from wavelengths of 100 nm to 1600 nm.
  • a negative resist is a resin whose solublity, in a given solvent, decreases upon exposure to electromagnetic radiation, preferably from wavelengths of 100 nm to 1600 nm.
  • a positve resist is a resin whose solublity, in a given solvent, increases upon exposure to electromagnetic radiation, preferably from wavelengths of 100 nm to 1600 nm.
  • photochemically effective amounts it is meant that the components of the photoinitiator system are present in amounts sufficient for the resin to undergo photochemical hardening upon exposure to light of the desired wavelength.
  • radical generator it is meant a species that generates a radical following an activation process.
  • activation processes can include, but are not limited to the following: heating; direct photoexcitation of the radical generator; indirect activation of the radical generator by energy transfer from another photoexcited species; transfer of an electron to or from the radical generator.
  • photo-activated radical generator it is meant a group that upon exposure to electromagnetic radiation generates a radical.
  • photo-activated radical generators include, but are not limited to the following species: Some examples of radical generators include: arylborate anions in the presence of a photosensitizer; benzoin; benzophenone; sulfonium ions; iodonium ions; acylphosphine oxides. Further examples of photo-activated radical generators can be found in: R. S. Davidson, J. Photochem. Photobiol. A: Chem. vol. 73 (1993) pp. 81-96; U.S. Pat. Nos.
  • an acid generator it is meant a species that generates a Br ⁇ nsted or Lewis acid following an activation process.
  • activation processes can include, but are not limited to the following: heating; direct photoexcitation of the acid generator; indirect activation of the acid generator by energy transfer from another photoexcited species; transfer of an electron to or from the acid generator.
  • photoacid generator it is meant a group that upon exposure to electromagnetic radiation generates a Br ⁇ nsted or Lewis acid.
  • photoacid generators include, but are not limited to the following species: sulfonium, selenonium, and iodinium salts, arene-iron cyclopentadienyl complexes, 4-nitrobenzylsulfonates and perfluorobenzylsulfonates (Shirai, M.; Tsunooka, M. Prog. Polym. Sci. 1996, 21, 1); dialkylphenacylsulfonium salts and 3,5-dialkyl-4-hydroxyphenyl sulfonium salts (Crivello, J. V.; Lee, J. L. Macromol. 1981, 14, 1141).
  • the present invention provides for compounds and/or compositions that have large two-photon or higher-order absorptivities, and which yield Lewis or Br ⁇ nsted acids (and/or radicals) after multi-photon excitation. It is preferable in the general design scheme of this invention that a multi-photon-excitable chromophore fragment and an acid-generating group are held in close proximity to one another (at a distance that is less than or equal to 20 ⁇ ). This can be achieved by connecting the chromophore and the acid generator using a covalent linkage, as illustrated in FIG. 1 . However, the invention is not limited to compositions of matter involving only a covalent linkage of the chromophore and acid generator.
  • the association mechanisms for the design scheme of FIG. 2 can include, but are not limited to, ion-pairing effects, hydrogen-bonding, charge-transfer complex formation, perfluoroaryl-aryl electrostatic interactions, ⁇ -stacking associations, coordinative-bond formation, and dipole-dipole pairing.
  • the molecule may be any two-photon dye skeleton, such as D- ⁇ -D, A- ⁇ -A, D-A-D or A-D-A, as described in U.S. Pat. No. 6,267,913, that is further derivatized with at least one photoacid generator or radical generator, such as either a sulfonium or an iodonium group.
  • the molecules of the invention can be described as a two-photon dye skeleton of the form D- ⁇ -D, A- ⁇ -A, D-A-D or A-D-A, that may have the following substituents:
  • one or more of the substituents pendant on the onium center may be part of a fused-ring structure, and two or more of the substituents may be joined through such a fused ring structure.
  • composition of matter numbers 84 and 87 are some preferred examples of such fused-ring onium photoacid generators.
  • the molecules of the invention preferably also have an anion to provide electroneutrality.
  • anions include: F ⁇ , Cl ⁇ , Br ⁇ , I ⁇ , CN ⁇ , SO 4 2 ⁇ , PO 4 3 ⁇ , CH 3 CO 2 ⁇ , CF 3 SO 3 ⁇ , NO 2 ⁇ , NO 3 ⁇ , BF 4 ⁇ , PF 6 ⁇ , SbF 6 ⁇ , AsF 6 ⁇ , SbCl 4 ⁇ , ClO 3 ⁇ , ClO 4 ⁇ , C(aryl) 4 ⁇ where aryl is an aryl group containing 25 or fewer carbon atoms (which range includes all values and subranges therebetween, including 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, and 25 as appropriate) and can be additionally substituted with one or more alky
  • the photoacid molecules will contain anions that are very weak Lewis bases that are effectively non-coordinating, such as BF 4 ⁇ , PF 6 ⁇ , SbF 6 ⁇ , AsF 6 ⁇ , B(aryl) 4 ⁇ or SbCl 4 ⁇ .
  • the invention molecules may also have a zwitterionic structure, wherein anions (such as B(aryl) 4 ⁇ ) are covalently bound to the cationic fragment, giving an overall electroneutral structure. Combinations of anions are possible.
  • the molecules of the invention should have the structure:
  • Ar 1 and Ar 2 can each independently be: a 5-membered heteroaromatic ring; a 6-membered aromatic ring; or a 6-membered heteroaromatic ring.
  • Ar 1 and Ar 2 can each independently be substituted with one or more H, alkyl, alkoxy, or aryl, which itself can be further substituted with one or more sulfonium, selenonium, iodonium, other acid- or radical-generating species, or monomer or pre-polymer functionalities.
  • R 1 , R 2 , R 3 , and R 4 can be independently alkyl or aryl, which can be further substituted with sulfonium, selenonium, iodonium, other acid- or radical-generating species, or a monomer or pre-polymer functionality.
  • Y is said counterion, and is one of the anions defined previously. The overall charge on the dye portion of the molecule is denoted by z.
  • pq is a positive integer less than 9 (which range includes all values and subranges therein, including 1, 2, 3, 4, 5, 6, 7, and 8).
  • the two or more substituents connected to a given aromatic ring may assume any substitution pattern.
  • the substitution pattern of the fragments R 1 R 2 X and the vinyl-group around Ar 1 may be ortho, meta, or para.
  • the molecules of the invention should have the structure:
  • Ar 1 and Ar2 can each independently be: a 5-membered heteroaromatic ring; a 6-membered aromatic ring; or a 6-membered heteroaromatic ring.
  • Ar 1 and Ar 2 can each independently be substituted with one or more H, alkyl, alkoxy, or aryl groups, which itself can be further substituted with one or more sulfonium, selenonium, iodonium, other acid- or radical-generating species, or monomer or pre-polymer functionalities.
  • R 1 and R 2 can be independently alkyl or aryl, which can be further substituted with sulfonium, selenonium, iodonium, other acid- or radical-generating species, or a monomer or pre-polymer functionality.
  • Y is said counterion, and is one of the anions defined previously.
  • the overall charge on the dye portion of the molecule is denoted by z.
  • the molecules should have the general structure:
  • Ar 1 and Ar 2 can each independently be: a 5-membered heteroaromatic ring; a 6-membered aromatic ring; or a 6-membered heteroaromatic ring.
  • Ar 1 and Ar 2 can each independently be substituted with one or more H, allcyl, alkoxy, or aryl groups, which itself can be further substituted with one or more sulfonium, selenonium, iodonium, other acid- or radical-generating species, or monomer or pre-polymer functionalities.
  • R 1 and R 2 can be independently H, alkyl or aryl, which can be further substituted with sulfonium, selenonium, iodonium, other acid- or radical-generating species, or a monomer or pre-polymer functionality. At least one of Ar 1 , Ar 2 , R 1 or R 2 must be substituted with a sulfonium, selenonium, or iodonium group, or other acid- or radical generating group. Y is said counterion, and is one of the anions defined previously. The overall charge on the dye portion of the molecule is denoted by z.
  • pq is a positive integer less than 9 (which range includes all values and subranges therein, including 1, 2, 3, 4, 5, 6, 7, and 8).
  • the molecules should have the general structure:
  • Ar 1 and Ar 2 can each independently be: a 5-membered heteroaromatic ring; a 6-membered aromatic ring; or a 6-membered heteroaromatic ring.
  • Ar 1 and Ar 2 can each independently be substituted with one or more H, alkyl, alkoxy, or aryl groups, which can be further substituted with sulfonium, selenonium, iodonium, other acid- or radical-generating species, or monomer or pre-polymer functionalities.
  • R 1 , R 2 , R 3 , and R 4 can be independently H, alkyl, or aryl, which can be further substituted with sulfonium, selenonium, iodonium, other acid- or radical-generating species, or a monomer or pre-polymer functionality. At least one of Ar 1 , Ar 2 , R 1 , R 2 , R 3 , or R 4 must be substituted with a sulfonium, selenonium, or iodonium group, or other acid- or radical generating group.
  • Y is said counterion, and is one of the anions defined previously.
  • the overall charge on the dye portion of the molecule is denoted by z.
  • pq is a positive integer less than 9 (which range includes all values and subranges therein, including 1, 2, 3, 4, 5, 6, 7, and 8).
  • the molecules should have the structure:
  • Ar 1 and Ar 2 can each independently be: a 5-membered heteroaromatic ring; a 6-membered aromatic ring; or a 6-membered heteroaromatic ring.
  • Ar 3 can be: a 5-membered heteroaromatic ring; a 6-membered aromatic ring; or a 6-membered heteroaromatic ring.
  • Ar 1 and Ar 2 can each independently be substituted with one or more H, alkyl, alkoxy, or aryl groups, which can be further substituted with sulfonium, selenonium, iodonium, other acid- or radical-generating species, or monomer or pre-polymer functionalities.
  • Ar 3 can be substituted with one or more H, acceptor, alkyl, alkoxy, or aryl groups, which can be further substituted with sulfonium, selenonium, iodonium, other acid- or radical-generating species, or monomer or pre-polymer functionalities.
  • R 1 and R 2 can be independently: alkyl or aryl which can be further substituted with sulfonium, selenonium, iodonium, other acid- or radical-generating species, or monomer or pre-polymer functionalities.
  • Y is said counterion, and is one of the anions defined previously.
  • the overall charge on the dye portion of the molecule is denoted by z.
  • the molecules should have the structure:
  • Ar 1 and Ar 2 can each independently be: a 5-membered heteroaromatic ring; a 6-membered aromatic ring; or a 6-membered heteroaromatic ring.
  • Ar 3 can be: a 5-membered heteroaromatic ring; a 6-membered aromatic ring; or a 6-membered heteroaromatic ring.
  • Ar 1 and Ar 2 can be substituted with one or more: H, alkyl, alkoxy, or aryl, which can be further substituted with sulfonium, selenonium, iodonium, other acid- or radical-generating species, or a monomer or pre-polymer functionality.
  • Ar 3 can be substituted with: one or more H, acceptor, alkyl, alkoxy, or aryl, which can be further substituted with sulfonium, selenonium, iodonium, other acid- or radical-generating species, or a monomer or pre-polymer functionality.
  • R 1 , R 2 , R 3 , and R 4 can be independently: alkyl, or aryl, which can be further substituted with sulfonium, selenonium, iodonium, other acid- or radical-generating species, or a monomer or pre-polymer functionality.
  • the overall charge on the dye portion of the molecule is denoted by z.
  • the molecules should have the structure:
  • Ar 1 and Ar 2 can each independently be: a 5-membered heteroaromatic ring; a 6-membered aromatic ring; or a 6-membered heteroaromatic ring.
  • Ar 3 can be: a 5-membered heteroaromatic ring; a 6-membered aromatic ring; or a 6-membered heteroaromatic ring.
  • Ar 1 and Ar 2 can each independently be substituted with: one or more H, alkyl, alkoxy, or aryl, which can be further substituted with sulfonium, selenonium, iodonium, other acid- or radical-generating species, or a monomer or pre-polymer functionality.
  • Ar 3 can be substituted with: one or more H, acceptor, alkyl, alkoxy, aryl, which can be further substituted with sulfonium, selenonium, iodonium, other acid- or radical-generating species, or a monomer or pre-polymer functionality.
  • R 1 and R 2 can be independently: H, alkyl, or aryl, which can be further substituted with sulfonium, selenonium, iodonium, other acid- or radical-generating species, or a monomer or pre-polymer functionality. At least one of Ar 1 , Ar 2 , Ar 3 , R 1 , or R 2 must be substituted with one or more sulfonium, selenonium, or iodonium groups, or other acid- or radical generating groups. Y is said counterion, and is one of the anions defined previously. The overall charge on the dye portion of the molecule is denoted by z.
  • pq is a positive integer less than 9 (which range includes all values and subranges therein, including 1, 2, 3, 4, 5, 6, 7, and 8).
  • the molecules should have the structure:
  • Ar 1 and Ar 2 can each independently be: a 5-membered heteroaromatic ring; a 6-membered aromatic ring; or a 6-membered heteroaromatic ring.
  • Ar 3 can be: a 5-membered heteroaromatic ring; a 6-membered aromatic ring; or a 6-membered heteroaromatic zing.
  • Ar 1 and Ar 2 can each independently be substituted with: one or more H, alkyl, alkoxy, or aryl, which can be further substituted with sulfonium, selenonium, iodonium, other acid- or radical-generating species, or a monomer or pre-polymer functionality.
  • Ar 3 can be substituted with: one or more H, acceptor, alkyl, alkoxy, or aryl, which can be further substituted with sulfonium, selenonium, iodonium, other acid- or radical-generating species, or a monomer or pre-polymer functionality.
  • R 1 , R 2 , R 3 , and R 4 can be independently: H, alkyl, or aryl, which can be further substituted with sulfonium, selenonium, iodonium, other acid- or radical-generating species, or a monomer or pre-polymer functionality. At least one of Ar 1 , Ar 2, Ar 3 , R 1 , R 2 , R 3 , or R 4 must be substituted with one or more sulfoniumn, selenonium, or iodonium groups, or other acid- or radical generating groups.
  • Y is said counterion, and is one of the anions defined previously.
  • the overall charge on the dye portion of the molecule is denoted by z.
  • Integer p is the charge on the counterion
  • pq is a positive integer less than 9 (which range includes all values and subranges therein, including 1, 2, 3, 4, 5, 6, 7, and 8).
  • the molecules should have the structure:
  • Ar 1 and Ar 2 can each independently be: a 5-membered heteroaromatic ring; a 6-membered aromatic ring; or a 6-membered heteroaromatic ring.
  • Ar 3 can be: a 5-membered heteroaromatic ring; a 6-membered aromatic ring; or a 6-membered heteroaromatic ring.
  • Ar 1 and Ar 2 can each independently be substituted with: one or more H, alkyl, alkoxy, or aryl, which can be further substituted with sulfonium, selenonium, iodonium, other acid- or radical-generating species, or a monomer or pre-polymer functionality.
  • Ar 3 can be substituted with: one or more H, acceptor, alkyl, alkoxy, or aryl, which can be further substituted with sulfonium, selenonium, iodonium, other acid- or radical-generating species, or a monomer or pre-polymer functionality.
  • R 1 , R 2 , R 3 , and R 4 can be independently: H, alkyl, or aryl, which can be further substituted with sulfonium, selenonium, iodonium, other acid- or radical-generating species, or a monomer or pre-polymer functionality. At least one of Ar 1 , Ar 2, Ar 3 , R 1 , R 2 , R 3 , or R 4 must be substituted with one or more sulfonium, selenonium, or iodonium gropus, or other acid- or radical generating groups.
  • Y is said counterion, and is one of the anions defined previously.
  • the overall charge on the dye portion of the molecule is denoted by z.
  • pq is a positive integer less than 9 (which range includes all values and subranges therein, including 1, 2, 3, 4, 5, 6, 7, and 8).
  • composition should contain one or more sensitizers selected from the group of molecules including:
  • Class 1 Structures Compounds where the end groups are electron donating groups
  • R a , R b , R c , R d are independently selected from the group including: H; a linear or branched alkyl group with up to 25 carbons; —(CH 2 CH 2 O) ⁇ —(CH 2 ) ⁇ OR a1 ; —(CH 2 CH 2 O) ⁇ —(CH 2 ) ⁇ NR a2 R a3 ; —(CH 2 CH 2 O) ⁇ —(CH 2 ) ⁇ CONR a2 R a3 ; —(CH 2 CH 2 O) ⁇ —(CH 2 ) ⁇ CN; —(CH 2 CH 2 O) ⁇ —(CH 2 ) ⁇ Cl; —(CH 2 CH 2 O) ⁇ —(CH 2 ) ⁇ Br; —(CH 2 CH 2 O) ⁇ —(CH 2 ) ⁇ I; —(CH 2 CH 2 O) ⁇ —(CH 2 ) ⁇ -Phenyl; various ary
  • composition may optionally and preferably contain a second component that can be selected from the group including a sulfonium salt such described in U.S. Pat. Nos. 5,302,757, 5,274,148, 5,446,172, 5,012,001, 4,882,201, 5,591,011, or 2,807,648, or an iodonium salt selected from the group including those described in C. Herzig and S. Scheiding, DE 4,142,327, CA 119,250,162 and C. Herzig, EP 4,219,376, CA 120,298,975 and U.S. Pat. Nos.
  • a second component that can be selected from the group including a sulfonium salt such described in U.S. Pat. Nos. 5,302,757, 5,274,148, 5,446,172, 5,012,001, 4,882,201, 5,591,011, or 2,807,648, or an iodonium salt selected from the group including those described in C. Herzig and S. Scheiding, DE 4,142,3
  • the anion for these salts be a nonnucleophilic anion such as BF 4 ⁇ , PF 6 ⁇ , SbF 6 ⁇ , AsF 6 ⁇ , or SbCl 4 ⁇ .
  • the two components of the photoinitiator system are preferably present in photochemically effective amounts, that is, amounts of each component sufficient to enable the resin to undergo photochemical hardening upon exposure to light of the desired wavelength.
  • the resin of the invention contains about 0.005 to about 10 parts (more preferably about 0.1 to about 4 parts) each of iodonium salt, sensitizer and donor.
  • the amounts of each component are independently variable and thus need not be equal, with larger amounts generally providing faster cure, but shorter shelf life. These ranges include all values and subranges therebetween, including 0.007, 0.01, 0.05, 0.07, 0.5, 0.7, 0.9, 1, 1.1, 2, 3, 4, 5, 6, 7, 8, 9, and 9.5 parts per 100 parts.
  • Patent 2,083,832 for use as triplet sensitizers for cyclo-addition reactions or for use as sensitizers for radical polymerization in combination with arylaminoacetic acids. References to these compounds are also found in Polym. Eng. Sci. 1983, 23, 1022-1024. This article mentions the utility of arninoketocoumarin compounds as sensitizers with alkoxypyridinium salts. Photoreactions of coumarin compounds are also mentioned in J. Org. Chem. 1984, 49, 2705-2708.
  • U.S. Pat. No. 4,250,053 teaches constrained coumarin as a sensitizer of iodonium salt for cationic polymerization.
  • the large electron affinity of the iodonium groups together with the electron-rich nature of the two-photon chromophores described in Class 1-I, Class 1-II, Class 1-III, and Class 1-IV above, strongly favors formation of a charge-transfer complex between the two-photon chromophores and the iodonium cation, which advantageously keep the species in close proximity, and which increases the efficiency of the two-photon and multi-photon induced sensitization process.
  • the invention includes compositions in which the multi-photon excitable molecular fragment may be a species other than those detailed above.
  • Preferred examples of alternative multi-photon-excitable molecular fragments include, but are not limited to the following species: Disperse Red 1 (Delysse, S.; Raimond, P.; Nunzi, J.-M., Chem. Phys. 1997, 219, 341); Coumarin 120, Rhodarnine B (Fischer, A.; Cremer, C.; Stelzer, E. H. K., Appl. Opt. 1995, 34, 1989); AF-50 (Mukheijee, N.; Mukheree, A.; Reinhardt, B.
  • the invention includes compositions in which the photoacid generator fragment may be a species other than those detailed above.
  • the photoacid generator fragment may be a species other than those detailed above.
  • alternative photoacid generator fragments include, but are not limited to the following species: 4-nitrobenzylsulfonates and perfluorobenzylsulfonates (Shirai, M.; Tsunooka, M. Prog. Polym. Sci. 1996, 21, 1); dialkylphenacylsulfonium salts and 3,5-dialkyl-4-hydroxyphenyl sulfonium salts (Crivello, J. V.; Lee, J. L. Macromol. 1981, 14, 1141).
  • the invention as described is not intended to be specific to any particularly mechanism of coupling between the two-photonabsorbing chromophore and the photoacid generating fragment.
  • Preferred examples of possible coupling mechanisms include electron-transfer, exciplex formation, and energy transfer.
  • One or more mechanisms can occur in the acid-generating photochemistry of a given molecule of the invention, and which mechanisms occur will depend upon the nature of the two-photon-absorbing chromophore and of the photoacid generating fragment.
  • such mechanisms of coupling can be used to generate radical species as well, as should be evident to one skilled in the art.
  • compositions of the invention are photoacid generator molecules that can be efficiently activated by multi-photon excitation.
  • the compositions themselves may exist as crystals, mesoscopic phases, polymers, glasses, liquids or gases.
  • the compositions may be used alone or in combination with other crystals, mesoscopic phases, polymers, glasses, liquids, or gases.
  • a particularly convenient and effective form of an optical element in accordance with the invention involves dispersing the multi-photon absorbing photoacids in a polymeric or prepolymeric binder.
  • the multi-photon absorbing photoacids can be mixed into the binder, or incorporated by grafting the chromophore onto the polymer, prepolymer or monomer constituents.
  • Preferable binders include, for example, polystyrene, polyacrylonitrile, polymethacrylate, poly(methyl methacrylate), poly(vinyl alcohol), copolymers of methyl methacrylate and methacrylic acid, copolymers of styrene and maleic anhydride and half ester-acids of the latter, as well as many others. Combinations are possible.
  • the polymeric binder be highly transparent so that the transparency of the molecules utilized in the practice of this invention can be advantageously employed.
  • the chromophores may still be excited by the two-photon or multi-photon absorption process.
  • the methods according to invention are carried out by converting a multi-photon absorbing molecule to an electronically excited state by absorption of at least two photons of radiation.
  • the generation of acid following excitation then facilitates numerous applications.
  • the molecule may be irradiated with visible, ultraviolet or infrared radiation.
  • the molecule is irradiated at wavelengths from 300 to 1100 nm, which range includes all values and subranges therebetween, including 400, 500, 600, 700, 800, 900, and 1000 nm.
  • the length and nature of the ⁇ -bridge and the strength and nature of the donor and/or acceptor groups it is possible to control several important molecular photophysical characteristics. These include, for example, the position and strength of the two-photon (or higher-order) absorption band(s), the energies of the lowest-occupied and highest unoccupied molecular orbitals, the excited-state lifetimes, and the fluorescence efficiency.
  • the composition of the ⁇ -conjugated bridge and the donor/acceptor groups can also be modified in such a way that the ease with which the material dissolves into a variety of host media—including liquids and polymeric hosts—is advantageously varied.
  • compositions of the type described above may, in principle, be used for the photo-activated transformation of any acid-modifiable host medium.
  • acid-modifiable materials include, but are not limited to: cationically polymerizable and cross-linkable media, catalyzed step-growth polymerizable and cross-linkable media, acid-cleavable ester-functionalized chemically amplified resins (as discussed in U.S. Pat. No. 6,136,500, herein incorporated by reference), polymerizable or cross-linkable materials containing acid-activated polymerization catalysts, and acid-sensitive biological media such as polypeptides and proteins. Preferred materials of these types are discussed in U.S. Pat. No. 5,514,728, which is incorporated herein by reference.
  • One especially preferable class of such materials includes monomers, oligomers, and or cross-linkable materials containing a cationically polymerizable group, such as epoxides, cyclic ethers, vinyl ethers, vinylamines, lactones, and cyclic acetals. Materials of this type are discussed in U.S. Pat. No. 5,514,728, incorporated herein by reference. Combinations are possible.
  • the molecules of this invention can be used for multi-photon-excitation initiated ring-opening methathesis polymerization ROMP). It is known that certain ROMP catalysts will initiate living ROMP of small-ring cyclic alkenes upon the introduction of acid (Lynn, D. M.; Mohr, B.; Grubbs, R. H.; Henling, L. M.; Day, M. W. J. Am. Chem. Soc. 2000, 122, 6601). Multi-photon activatable ROMP can then be achieved by irradiating a mixture containing a ROMP medium to which has been added the molecules of this invention.
  • Onium salts are also well known to generate radicals which can activate free radical polymerization and cross-linking.
  • the molecules of the invention can also be used for the photopolymerization and photo-crosslinking of free-radical-polymerizable compounds.
  • Compounds of this type contain at least one ethylenically unsaturated double bond. Some preferred examples include monomers, oligomers, and cross-linkable polymers containing acrylate, methacrylate, acrylamide, methacrylamide, and vinyl functionalities. Free-radical-polymerizable compounds are described in U.S. Pat. No. 5,514,728, incorporated herein by reference.
  • the resins are termed negative resists.
  • negative resist Preferable examples of negative resist that could be used in accord with this invention are described in U.S. Pat. Nos. 5,463,084, 5,639,413, 6,268,403, 4,689,289, 4,069,056, 4,102,687, 4,069,055, 4,069,056, 4,058,401, 4,058,400, 5,086,192, 4,791,045, 4,090,936, 5,102,772, and 5,047,568, and patents cited therein—which are incorporated herein by reference.
  • Postive resists are well known to those skilled in the art of lithography and may be used in accord with this invention, and some preferred examples are described in U.S. Pat. Nos. 6,346,363 and 6,232,417 which are incorporated herein by reference.
  • the compositions of the invention can generate both acid and radical species. The tendency of a certain molecule of the invention to generate radicals versus acid will depend upon the specific molecular structure and the medium in which the molecule is dispersed.
  • Acid generation is favored in cases, among other known to those skilled in the art, for which the molecules selected from those of the invention bear groups which upon protonation have pKa's less than or equal to 2. Acid generation is disfavored in cases for which the molecules selected from those of the invention bear groups which upon protonation have pKa's greater than 2.
  • compositions of matter described in this invention also provide a means for the direct fabrication of complex microstructures from ceramic materials.
  • the prepolymer may be a free-radical-polymerizable species (acrylate, acrylamide, etc.), as described in U.S. Pat. No. 6,117,612, or cationically polymerizable media (epoxides, vinyl ethers, cycle ethers, etc.), the use of which is not described in U.S. Pat. No. 6,117,612.
  • acrylate, acrylamide, etc. as described in U.S. Pat. No. 6,117,612
  • cationically polymerizable media epoxides, vinyl ethers, cycle ethers, etc.
  • two-photon or multi-photon initiators may be used for two-photon (multi-photon) generation of charge carriers, including protonic conductivity, for example in photorefractive polymers.
  • the invention two-photon or multi-photon initiators may be used for two-photon or multi-photon initiated polymerization.
  • the invention two-photon or multi-photon initiators may be used for photoinduced cleavage of activated ester functionalities (such as tert-butoxy, tetrahydropyranyl, etc.).
  • the invention two-photon or multi-photon initiators may be used to initate changes in a host medium to write holographic information.
  • the invention two-photon or multi-photon initiators may be used for two-photon or multi-photon optical lithography and three-dimensional optical memory.
  • the invention two-photon or multi-photon initiators may be used for microfabrication of three-dimensional objects.
  • the invention two-photon or multi-photon initiators may be used to alter the pH of an arbitrary medium.
  • the invention two-photon or multi-photon initiators may be used for in vivo or in vitro decaging of biochemical agents for biological, physiological, or medicinal purposes, including drug delivery and photodynamic therapy.
  • the invention two-photon or multi-photon initiators may be used for modifying and functionalizing an arbitrary surface, photoresist patterning and processing, surface inking, and patterning printing plates.
  • the invention two-photon or multi-photon initiators may be used for modifiing, functionalizing, or texturing the surface or sub-surface of a biological tissue, with the aim, for example, of culturing the growth of cells, or modifying and engineering tissues.
  • the invention two-photon or multi-photon initiators may be used to photoactivate reactions which destablize liposome membranes, which in turn may be used for drug delivery, photodynamic therapy, and decaging of agents in diagnostic assays.
  • the invention two-photon or multi-photon initiators can be used for the fabrication or articles using single-beam tightly focused (numerical aperture of 0.2 to 1.4) laser exposure.
  • the invention two-photon or multi-photon initiators can be used for the fabrication of three-dimensional objects having 1, 2, and 3-dimensional periodicities using multiple-beam-holographic interference exposure.
  • the invention two-photon or multi-photon initiators can be used for the fabrication of articles having linear dimensions or feature sizes ranging from 10 centimeters to 20 nanometers, depending upon the specific optical excitation geometry employed.
  • a photo-pattemable medium containing two or more of the two-photon or multi-photon initiators can be exposed sequentially or in parallel using different excitation wavelengths to impress two or more three-dimensional patterns into the same medium, and thereby produce a single complex three-dimensional object.
  • a series of one or more photo-patternable media containing one or more of the two-photon or multi-photon initiators can be used to photo-pattern a single complex three-dimensional object comprised of two or more distinct material systems.
  • a composite medium consisting of (a) the compositions of the invention and (b) a self-assembling or self-organizing material (see below), can be photo-patterned by two- or multi-photon excitation to generate an article having structure, possibly on very different length-scales, defined by (1) the impressed photo-pattern and (2) the structure associated with the self-assembled units.
  • self-assembling or self-organizing materials include, but are not limited to, the following: metal, semiconductor, and metal oxide nanoparticles; polymer, silica, and metal oxide microspheres; block co-polymers that spontaneously form ordered structures (e.g. lamellae or micro-domains); liquid crystals and liquid-crystal polymers in various phases; colloidal crystal arrays; lipid-bilayer systems ordered in various phases (e.g. vesicle, hexagonal, or columnar).
  • the multi-photon activatable materials described in this section can be used for the three-dimensional microfabrication of a wide range of complex devices and systems.
  • Preferred examples include micro-electromechanical structures, micro-electrooptic systems, optical waveguides, photonic circuits, optical component couplers, micro-optical switching systems, microfluidic devices (such as disclosed in U.S. Pat. No. 6,136,212, which is incorporated herein by reference), and the construction of complex patterns and structures used as templates or microscaffolds in further fabrication processes.
  • the sulfonium group(s) can be attached to various sites on triphenylamines; for example, in the examples in Scheme 1 the sulfonium group is attached to the meta position of a phenyl ring on the donor nitrogen atom.
  • the molecules described in Scheme 1 are highly efficient cationic photoinitiators with quantum yields of photoacid generation of ⁇ 0.5, independent of the counter-ion.
  • the sulfonium group can be attached to a two-photon dye by a covalent bond, as shown for the molecules in Scheme 2.
  • the sulfonium group can be attached to various sites in the molecule, as will be described, but, in the examples shown in Scheme 2, the sulfonium group is attached to the meta position of a terminal phenyl group.
  • Our experiments have shown that molecules described in this scheme are effective as initiators for the photopolymerization of a wide range of epoxides, including cyclohexene oxide, 4-vinyl-cyclohexene diepoxide, EPON SU-8, and ARALDITE CY179MA.
  • the precursor sulfides for bis(styryl)benzene sulfonium salts (type-I) 41 and 42 were synthesized using a phase-transfer Homer-Emmons reaction and Pd-catalyzed C—N coupling reactions (Scheme 3).
  • D-A-D type chromophores have large two-photon cross sections, and since the sulfonium group is a relatively strong electron acceptor, four D-A-D type bis(styryl)benzene molecules with sulfonium on the central ring and electron-donating alkoxy or amino donors on both ends were prepared. To increase the solubility of these species, long allyl chains were attached. Introduction of the alkoxy group as the donor shifts the molecules' absorption peaks to shorter wavelength, which could be advantageous for certain applications.
  • Triphenylsulfonium salts are known as UV sensitive cationic and radical initiators; like dialkyl sulfonium salts they can be attached to appropriate chromophore so that they act as photo-initiators via an electron transfer process.
  • Phenothiazine the first compound in Scheme 10, with N and S atoms in the central of three fused rings, is the basis of one method of attachment of a triphenylsulfonium group to a two-photon chromophore.
  • the sulfur can be arylated to sulfonium and the secondary amino group affords a site for the extension of a conjugated system, such as those characteristics of D- ⁇ -D two-photon absorbing chromophores.
  • the molecules (84, 87) were prepared by first arylating the amine, using a palladium-catalyzed coupling reaction, and then arylating the sulfide using an iodonium salt.
  • 87 can efficiently initiate both cationic and radical polymerization as shown in FIG. 5 .
  • a triarylamine-triarylsulfonium (Scheme 11) was also prepared in four steps. 3-bromophenylphenylsulfide was synthesized according to literature procedures. It was found that 91 is less active than dialkylsulfonium triphenylamine.
  • Stilbene dye-triphenylsulfonium compound 100 has been prepared in seven steps. Formylation of N,N-dibutylaniline gave 4-N,N-dibutylamino benzaldehyde (92) in a yield of 79.9%. Reduction of aldehyde 92 with NaBH 4 gave 4-N,N-dibutylamino benzylalcohol (93) in a yield of 89.4%. The preparation of 4-N,N-dibutylamino benzylchloride from alcohol 93 was unsuccessful using thionyl chloride (SOCl 2 ).
  • Bistyiylbenzene dye-sulfonium compound 106 was prepared in six steps. In order to increase solubility of the compound, n-butyl substituents were employed on the nitrogen, along with two methoxy groups on the central ring. 1,4-dimethoxyl benzene reacted with formaldehyde in concentrated hydrochloric acid in the presence of hydrogen chloride gas to give 2,5-di(chloromethyl)-1,4-dimethoxyl benzene 101 in a yield of 56.2%. The reaction of 101 with triethylphosphite gave tetraethyl 2,5-bismethoxyl-p-xylene phosphonate (102) in a yield of 94.3%.
  • Scheme 14 shows the synthesis of a precursor suitable for conversion to a two-photon dye doubly functionalized with triarylsulfonium groups.
  • Scheme 15 shows examples of two-photon chromophores containing the julolidine that have been synthesized and that are potential two-photon sensitizers with diphenyliodonium salts through a charge-transfer interaction.
  • Scheme 16 summarizes acid quantum-yield data for some of the photoacids described above.
  • FIG. 3 shows a comparison of the photopolymerization of cyclohexene oxide using 5, 7, 8 and 9 as initiators.
  • Sulfonium salt 5 which has a triflate counterion, does not initiate polymerization, even after one hour of irradiation.
  • 8 and 9 having a SbF 6 ⁇ anion, rapidly initiate polymerization, leading to 90% conversion to polymer in 130 seconds.
  • 8 and 9 were found to initiate polymerization with extremely short induction times relative to triphenylsulfonium hexafluoroantimonate (TPS), when irradiated at 300 nm, under otherwise identical conditions.
  • TPS triphenylsulfonium hexafluoroantimonate
  • a typical formulation of epoxy acrylate CN 115 (Sartomer Company, Inc.), initiator, and tetrahydrofuran (20% by weight of CN115) was used for radical polymerization experiments and the conversion of acrylate was monitored using IR spectroscopy at 810 cm ⁇ 1 .
  • mono- or bi-molecular systems of dye/sulfonium salt undergo inter- or intra-molecular electron-transfer reactions to produce the active phenyl radical species, and the radical cation of the dye. The latter might further undergo a secondary reaction to form colorless photo-products, while the phenyl radical can initiate a radical polymerization of unsaturated acrylates or resins.
  • FIG. 5 illustrates radical polymerization initiated by compound 87.
  • the plots of conversion vs. irradiation time show that both the combination systems 99 or 105 with triphenylsulfonium hexafluorophosphate (TPS′), and the single molecule systems 100 or 106 are more effective than 99 or 105 alone.
  • TPS′ triphenylsulfonium hexafluorophosphate
  • single molecule systems 100 and 106 are the most efficient initiators, and both the polymerization rate (initial slope of a curve) and maximal conversion are higher than for others under the same conditions.
  • the polymerization rate also decreases with the decrease of concentration of initiator 100 or 106, but not dramatically.
  • the concentration of the components of the bimolecular system has a dramatic influence on the polymerization
  • the decrease of concentration of 99, 105 or sulfonium (TPS) leads to a significant increase of the induction time, a decrease of polymerization rate, and a decrease in maximal conversion. Therefore, the single molecule dye-sulfonium linked radical initiators are highly efficient in viscous media.
  • Preferable high peak-power lasers (emission wavelengths, and pulse durations) suitable for two-photon/multiphoton excitation of photoacid- and radical-generators include:
  • OPA optical parametric amplifier
  • Nd:yttrium vanadate Nd:YVO 4
  • Nd:yttrium lanthanum fluoride Nd:YLF 4
  • the two-photon absorption cross-sections, ⁇ are measured by the two-photon induced fluorescence method (Xu, C.; Webb, W. W. J. Opt. Soc. Am. B, 1996,13, 481-491) using both femtosecond and nanosecond pulsed lasers as excitation sources.
  • the reference standards used in the measurement of ⁇ are (1,4-bis(2-methylstyrl)benzene in cyclohexane, rhodamine B in methanol, fluorescein in pH 11 water, and coumarin 307 in methanol), for which the two-photon properties have been well characterized in the literature (Xu, C.; Webb, W. W., J. Opt. Soc. Am. B, 1996, 13, 481-491; Kennedy, S. M.; Lytle, F. E. Anal Chem., 1986, 58, 2643-2647).
  • the ⁇ for a given compound is obtained from experimentally determined parameters using:
  • ⁇ s S s ⁇ ⁇ r ⁇ ⁇ r ⁇ C r S r ⁇ ⁇ s ⁇ ⁇ s ⁇ C s ⁇ ⁇ r
  • S the detected two-photon induced fluorescence signal
  • the fluorescence quantum yield
  • C the concentration of the chromophore
  • is the collection efficiency of the experimental setup and accounts for the wavelength dependence of the detectors and optics as well as the difference in refractive indexes between the solvents in which the reference (r) and sample (s) compounds are dissolved.
  • the measurements are conducted in a regime where the fluorescence signal shows a quadratic dependence on the intensity of the excitation beam, as expected for two-photon induced emission.
  • the nanosecond-pulse measurements are performed using an experimental set-up described previously (Rumi, M; Ehrlich, J. E; Heikal, A. A.; Perry, J. W.; Barlow, S.; Hu, Z.; McCord-Maughon, D.; Parker, T. C.; Röckel, H.; Thayumanavan, S.; Marder, S. R.; Beljonne, D.; and Brédas, J.-L. J. Am. Chem. Soc., 2000, 122, 9500-9510).
  • the excitation source is a Nd:YAG-pumped optical parametric oscillator (Quanta-Ray, MOPO 730) with a 5-ns pulse duration and 10 Hz repetition rate, tunable over the wavelength range of 430-700 and 730-2000 nm.
  • a two-arm set-up is used to correct for fluctuations in the laser intensity.
  • the beam is approximately collimated over the 1-cm pathlength of the glass cuvette.
  • the concentrations of the solutions are ⁇ 10 ⁇ 4 M for both the sample and reference compounds.
  • the two-photon-induced fluorescence is collected at right angles to the excitation beam and focused onto a photomultiplier tube (PMT).
  • Short wave pass filters are used to block scattered light. The signals are averaged over about 300 pulses.
  • the femtosecond-pulse measurements are performed using a Ti:Sapphire laser (Spectra-Physics, Tsunami) as the excitation source.
  • This laser generates ⁇ 100 fs pulses at a repetition rate of 82 MHz in the wavelength range of 710-1000 nm.
  • a one-arm set-up is utilized in this experiment, and the sample and reference measurements are taken in series for each excitation wavelength.
  • the beam is focused into a 1-cm pathlength cell containing solutions at concentrations of 10 ⁇ 4 M-10 ⁇ 6 M. Fluorescence is detected at 90° with respect to the excitation beam by a PMT after a series of short-wave-pass filters and a monochromator to block out scattered light.
  • the fluorescence collection is performed at the same detection wavelength for reference and sample compounds.
  • the PMT is operated in a single photon counting regime and its output is amplified and read by a frequency counter. The output signal is averaged for 30 seconds and recorded.
  • the magnitude of the two-photon absorptivity of a generic medium can be characterized by the two-photon absorption coefficient, ⁇ (having units of, e.g., cm/W).
  • is a macroscopic property of a given material that depends upon the specific composition.
  • can be measured using several techniques, including nonlinear transmission and “Z-scan”, as described in R. L. Sutherland's Handbook of Nonlinear Optics (New York, Marcel Dekker, 1996).
  • composition of matter which includes a sulfonium, selenonium, iodonium salt, or other acid- or radical generator containing:
  • composition of matter which includes a sulfonium, selenonium, or iodonium salt, or other acid- or radical generator containing:
  • composition of matter which includes a sulfonium, selenonium, or iodonium salt, or other acid- or radical generator containing:
  • composition according to embodiment A above in which a two-photon absorbing chromophore with a two-photon cross-section >50 ⁇ 10 ⁇ 50 cm 4 s/photon, wherein the excited state of the chromophore can activate the radical/acid generator towards undergoing a molecular rearrangement generating a Br ⁇ nsted or Lewis acid and/or radical, and the chromophore is a molecule in which two donors are connected to a conjugated ⁇ -electron bridge (abbreviated “D- ⁇ -D” motif).
  • composition according to embodiment A above in which a two-photon absorbing chromophore with a two-photon cross-section >50 ⁇ 10 ⁇ 50 cm 4 s/photon, wherein the excited state of the chromophore can activate the radical/acid generator towards undergoing a molecular rearrangement generating a Br ⁇ nsted or Lewis acid and/or radical, and the chromophore is a molecule in which two donors are connected to a conjugated ⁇ -electron bridge which is substituted with one or more electron accepting groups (abbreviated “D-A-D” motif).
  • D-A-D electron accepting groups
  • composition according to embodiment A above in which a two-photon absorbing chromophore with a two-photon cross-section >50 ⁇ 10 ⁇ 50 cm 4 s/photon, wherein the excited state of the chromophore can activate the radical/acid generator towards towards undergoing a molecular rearrangement generating a Br ⁇ nsted or Lewis acid and/or radical, and the chromophore is a molecule in which two acceptors are connected to a conjugated ⁇ -electron bridge (abbreviated A- ⁇ -A” motif).
  • composition according to embodiment A above in which a two-photon absorbing chromophore with a two-photon cross-section >50 ⁇ 10 ⁇ 50 cm 4 s/photon, wherein the excited state of the chromophore can activate the radical/acid generator towards undergoing a molecular rearrangement generating a Br ⁇ nsted or Lewis acid and/or radical, and the chromophore is a molecule in which two acceptors are connected to a conjugated ⁇ -electron bridge which is substituted with one or more electron donating groups (abbreviated “A-D-A” motif).
  • a method of generating a Br ⁇ nsted or Lewis acid or radical which includes a step of exposing a compound that includes a sulfonium, selenonium, or iodonium salt, or other acid- or radical generator; a chromophore having the formula D 1 - ⁇ -D 2 wherein D 1 and D 2 are electron donor groups; and 7 includes a bridge of ⁇ -conjugated bonds connecting D 1 and D 2 ; and a group which links the chromophore to the radical/acid generator, bringing the chromophore and the radical/acid generator into close spatial proximity; and an anion;to pulsed laser radiation and converting the compound to a multi-photon electronically excited state upon simultaneous absorption of at least two photons of the radiation by the compound, wherein the sum of the energies of all of the absorbed photons is greater than or equal to the transition energy from a ground state of the compound to the multi-photon excited state, and wherein the energy of each absorbed photo
  • a method of generating a Br ⁇ nsted or Lewis acid and/or radical which includes:
  • 3-bromothioanisole (1) 3-bromobenzenethiol (5 g, 26.44 mmol) was added to a solution of sodium methoxide (1.43 g, 26.48 mmol) in 20 ml of anhydrous methanol. The mixture was stirred for 30 min under nitrogen at room temperature and a solution of methyl iodide (4.51 g, 31.77 mmol) in 20 ml anhydrous methanol was then added. The reaction mixture was stirred overnight at room temperature, poured into 2 M aqueous NaOH solution (30 ml) and extracted three times with ether (60 ml ⁇ 3).
  • 3-bromothioanisole (1) (2.0 g, 9.85 mmol) was added to a solution of tris(dibenzylideneacetone)dipalladium (Pd 2 (dba) 3 ) (0.28 g, 0.306 mmol) and bis(diphenylphosphino)ferrocene (IPPF) (0.245 g, 0.442 mmol) in dry toluene (20 mL) under a nitrogen atmosphere at room temperature. The resultant mixture was stirred for 10 minutes.
  • trans-4,4′-dibromostilbene 10
  • 14 50% aqueous sodium hydroxide (20 ml) was added to a solution of diethyl 4bromobenzyl phosphnate (5.66 g, 18.4 mmol) and 4-bromobenzaldhyde (3.41 g, 18.4 mmol) in benzene (20 ml).
  • Tetra-(n-butyl) ammonium iodide (420 mg) was added and the mixture was refluxed under nitrogen for 30 min.
  • the reaction mixture was allowed to cool and diluted by addition of water (50 ml).
  • a white solid was collected, washed with methanol and ether, and isolated in 51.0% (3.17 g) yield.
  • trans-4,4′-di(phenylamino)stilbene (11).
  • trans-4,4′-di(p-n-butylphenyl)aminostilbene (12).
  • DPPF bis-(diphenylphosphino)ferrocene
  • the yellow oil was allowed to cool at 0° C. to become a yellow solid.
  • the yellow solid was collected by filtration and washed four times with water and three times with ether.
  • a NMR-pure product was obtained without further purification and in 77.4% (0.72 g) yield.
  • E,E-1,4-Bis(p-bromostyryl)benzene (26). 50% aqueous sodium hydroxide (20 ml) was added to a solution of tetraethyl p-xylylenebisphosphonate (2.40 g, 6.35 mmol) (25) and 4-bromobenzaldehyde (2.41 g, 13.02 mmol) in 10 ml of benzene. Tetra-n-butylammonium iodide (148 mmg) was added and the mixture was refluxed under nitrogen for 1 hour. The reaction mixture was allowed to cool and diluted by the addition of water (25 ml). A yellow solid was collected and washed three times with water, methanol and ether. The product was purified by recrystallization from xylenes and was isolated in 61.9% (1.73 g) yield (Product is insoluble in standard solvents).
  • the mixture was allowed to cool, poured into 20 ml of water and extracted three times with ether (60 ml ⁇ 3). The combined organic layer was dried over anhydrous magnesium sulfate. After removal of solvent under reduced pressure, the product was purified by flash column chromatography using 5% of ethyl acetate in hexanes as eluant. The product was further purified by recrystallization from the mixture solvent of ether and hexanes (1:5) and was isolated in 9.2% (0.28 g) yield.
  • E,E-1,4-Bis ⁇ p-[N-(4-n-butylphenyl)-N-(3-methylthiophenyl)]aminostyryl ⁇ benzene (37) (0.27 g, 0.33 mmol) was dissolved in 10 ml of dry methylene chloride and cooled at ⁇ 78° C. To this solution was added via syringe methyl trifluoromethanesulfonate (82.7 ⁇ l, 0.73 mmol) and stirred for 30 min while the temperature was maintained at ⁇ 78° C. Then the mixture was stirred for two hours at room temperature. The solvent was removed under reduced pressure, and metathesis of anion was performed without isolation of the product.
  • E,E-1,4-Bis ⁇ p-[N-(4-n-butylphenyl)-N-(3-benzylthio phenyl)]amino styryl ⁇ benzene (38) (0.59 g, 0.61 mmol) was dissolved in 10 ml of dry methylene chloride and cooled at ⁇ 78° C. To this solution was added via syringe methyl trifluoromethanesulfonate (145 ⁇ l, 1.28 mmol). While maintaining that temperature, the mixture was stirred for 30 min. Then the mixture was stirred for two days at room temperature. The solvent was removed under reduced pressure and, metathesis of anion was performed without isolation of the product.
  • E,E-1,4-Bis[2′-methylthio-4′-(N,N-di-p- n butylphenyl)amino styryl]benzene (48) (1.23 g, 1.32 mmol) was dissolved in 30 ml of dry methylene chloride and cooled at ⁇ 78° C. To this solution was added via syringe methyl trifluoromethanesulfonate (310 ⁇ l, 2.74 mmol) and stirred for 30 min. while the temperature was maintained at ⁇ 78° C. Then the mixture was stirred for two days at room temperature. The solvent was removed under reduced pressure and metathesis of anion was performed without isolation of the product.
  • E,E-1,4-Bis[2′-benzyl thio-4′-(N,N-di-p-n-butylphenyl)amino styryl]benzene (49) (1.47 g, 1.35 mmol) was dissolved in 25 ml of dry methylene chloride and cooled at ⁇ 78° C. To this solution was added via syringe methyl trifluoromethanesulfonate (331 ⁇ l, 2.93 mmol). While maintaining that temperature, the mixture was stirred for 30 min. Then the mixture was stirred for two days at room temperature. The solvent was removed under reduced pressure and metathesis of anion was performed without isolation of the product.
  • the isomers were purified by flash chromatography using hexanes/methylene chloride/ethyl acetate (50:40:10) as eluant.
  • the isomers were dissolved in 30 ml of toluene and refluxed with a small crystal of iodine for 20 hours. The mixture was cooled to ambient temperature and brownish crystals were formed. The brownish crystals were refluxed with activated charcoal in 40 ml of toluene for 20 min and the resulting yellow crystals were collected after hot-filtration in 47.6% (0.53 g) yield.
  • the reaction was quenched by addition of 40 ml of water.
  • the mixture was extracted three times with 70 ml of ether and the combined organic layer was dried over anhydrous magnesium sulfate. After removal of solvent, the product was purified by recrystallization from methanol to give a yield of 2.05 g (74.2%).
  • the aqueous layer was extracted three times with 20 ml of ether, and the combined organic layer was washed three times with 20 ml of saturated brine and dried over anhydrous sodium sulfate. After removal of solvent, the residue was recrystallized from toluene and was isolated in 0.21 g (41.3%) yield.
  • Photopolymerizations initiated by one-photon excitation. Aliquots (1.25 ml) of a 10 ml of solution containing 0.0791 mmol of sulfonium salt, such as 7, 8, 9, 23, 41, 52, or 61 and 8 ml of cyclohexene oxide (7.76 g, 0.0791 mol) in methylene chloride were sealed in 4-ml Pyrex vials with caps and irradiated with a 419 nm photochemical lamp in a merry-go-round holder. After various intervals the sample tubes were withdrawn from the irradiation chamber and any ionic reactions were immediately quenched by the addition of 2M ammonia solution in methanol (1 ml).
  • sulfonium salt such as 7, 8, 9, 23, 41, 52, or 61 and 8 ml of cyclohexene oxide (7.76 g, 0.0791 mol) in methylene chloride were sealed in 4-ml Pyrex vials
  • the polymers were precipitated by addition to methanol, collected by filtration and dried in vacuo for 40 hours.
  • the plots of time versus conversion is shown in FIGS. 3 and 4 (above) demonstrate that each of the salts described in this example of efficient initiators for cationic polymerization.
  • the quantum yield for photochemical generation of acid, ⁇ H + was obtained from measurements of the acid generated when a 4.0 ⁇ 10 ⁇ 4 M solution of a PAG in acetonitrile was one-photon excited by irradiation at 400 nm using either the monochromated output of a xenon lamp or a frequency-doubled mode-locked Ti:sapphire laser. At this concentration more than 99% of the incident photons were absorbed.
  • the photogenerated acid was titrated by the addition of excess rhodamine B base in acetonitrile (6.0 ⁇ 10 ⁇ 5 M after addition) and quantified spectrophotometrically from the absorbance of protonated rhodamine B base.
  • the up-converted fluorescence was detected at 520 nm and its intensity was proportional to the square of the excitation power, as expected for two-photon absorption (TPA).
  • concentration of the photogenerated acid, [H + ] was determined spectrophotometrically following a 30-minute exposure.
  • the relative acid-yield efficiency at each wavelength was calculated by dividing [H + ] by the ratio of the emission counts and the TPE action cross-section of the fluorescein reference ( ⁇ F(t)>/ ⁇ f ⁇ ) ref (to account for the temporal and spatial dependence of the excitation intensity as a function of wavelength) and normalizing to ⁇ of 41 at 705 nm.
  • the TPE and the acid-yield efficiency spectra are shown in FIG. 7 .
  • the TPE and acid-yield efficiency spectra exhibit similar features, and the acid-yield at 745 nm increases quadratically with excitation power, as expected for a photochemical process activated by TPA.
  • the threshold power for the onset of polymerization within a 10-second exposure was established at 710 and 760 nm by the advent of a circular diffraction pattern in the far-field of the transmitted beam.
  • the threshold powers were 2.4 mW (41), 44 mW (CD1012/ITX), and 212 mW (CD1012).
  • the available power (317 mW) was insufficient to initiate polymerization of the TPS and DPI-DMAS resins.
  • the threshold powers were 5.6 mW (41), 50 mW (CD1012/ITX), 468 mW (DPI-DMAS), and 560 mW (CD1012).
  • the available power (655 mW) was not adequate to initiate polymerization of the TPS resin.
  • the threshold powers were 1.7 mW (41), 4.4 mW (23), 33 mW (CD1012/ITX), and 185 mW (CD1012).
  • the available power (317 mW) was insufficient to initiate polymerization of the TPS and DPI-DMAS resins.
  • the threshold powers were 4.7 mW (41), 6.4 mW (23), and 45 mW (CD1012/ITX).
  • the available power (655 mW) was not adequate to initiate polymerization of the CD1012, DPI-DMAS, and TPS resins.
  • the threshold measurements show that the two-photon sensitivity of 23 and 41 is nearly one order of magnitude greater than that of the best-performing conventional initiator, (CD1012/ITX), and more than two orders of magnitude greater than that of TPS.
  • the resulting solid film had a thickness of 330 ⁇ 100 ⁇ m.
  • the film was exposed in a target three-dimensional pattern by tightly focusing 80-fs pulses from a Ti:sapphire laser at a wavelength of 745 nm into the resin while translating the focal point at a speed of 50 ⁇ m/s (60 ⁇ /1.4 N.A. oil-immersion objective, 82-MHz pulse repetition rate).
  • the average optical power at the film was varied between 1-5 mW.
  • the film was immersed in ⁇ -butyrolactone for 60 minutes to remove the unexposed resin, and then rinsed with methanol, leaving the microstructures shown in FIG. 9 standing freely on the substrate.
  • the resulting solid film had a thickness of 330 ⁇ 100 ⁇ m.
  • the film was exposed in a target three-dimensional test-pattern by tightly focusing 70-fs pulses from a Ti:sapphire laser at a wavelength of 730 mn into the resin while translating the focal point at a speed of 50 ⁇ m/s (60 ⁇ /1.4 N.A. oil-immersion objective, 82-MHz pulse repetition rate). Following irradiation, the film was immersed in ⁇ -butyrolactone for 60 minutes to remove the unexposed resin, and then rinsed with methanol, leaving free-standing microstructures where the average exposure power was suitably high. Inspection of the sample before and after developing with ⁇ -butyrolactone revealed that the resin was damaged for average optical powers exceeding 17 ⁇ 2 mW, and the threshold power for polymerization was 0.3 ⁇ 0.1 mW.
  • the resulting solid film had a thickness of 330 ⁇ 100 ⁇ m.
  • the film was exposed in a target three-dimensional test-patent by tightly focusing 70-fs pulses from a Ti:sapphire laser at a wavelength of 730 nm into the resin while translating the focal point at a speed of 50 ⁇ m/s (60 ⁇ /1.4 N.A. oil-immersion objective, 82-MHz pulse repetition rate). Following irradiation, the film was immersed in ⁇ -butyrolactone for 60 minutes to remove the unexposed resin, and then rinsed with methanol, leaving free-standing microstructures where the average exposure power had been suitably high. Inspection of the sample before and after developing with ⁇ -butyrolactone revealed that the resin was damaged for average optical powers exceeding 17 ⁇ 2 mW, and the threshold power for polymerization was 1.3 ⁇ 0.3 mW.
  • the resulting solid film had a thickness of 230 ⁇ 100 ⁇ m.
  • the film was exposed in a target three-dimensional test-pattern by tightly focusing 70-fs pulses from a Ti:sapphire laser at a wavelength of 720 nm into the resin while translating the focal point at a speed of 50 ⁇ m/s (60 ⁇ /1.4 N.A. oil-immersion objective, 82-MHz pulse repetition rate). Following irradiation, the film was immersed in ⁇ -butyrolactone for 60 minutes to remove the unexposed resin, and then rinsed with methanol, leaving free-standing microstructures where the average exposure power was suitably high. Inspection of the sample before and after developing with ⁇ -butyrolactone revealed that the resin was damaged for average optical powers exceeding 17 ⁇ 2 mW, and the threshold power for polymerization was ⁇ 7 mW.
  • Fabrication of sub-millimeter columnar structures by two-photon polymerization of a liquid epoxide resin containing PAG 41 using nanosecond laser pulses A cell was fashioned by sandwiching a 2-mm thick o-ring between two glass substrates, one of which was treated with a trimethoxy[2-(7-oxabicyclo[4.1.0]hept-3-yl)ethyl]silane adhesion promoter. The cell was filled with 10.3 mM 41 in 20%/80% EPON SU-8/4-vinyl-1-cyclohexene diepoxide (1.26 wt.-% PAG).
  • FIG. 10 shows a scanning electron micrograph of the columns. The width of the smallest feature was 60 ⁇ m.
  • the resulting solid film had a thickness of 330 ⁇ 100 ⁇ m.
  • Several regions of the film were then irradiated with focused 5-ns laser pulses at a wavelength of 745 nm (10-Hz repetition rate; 500-mm focal length lens; 5-mm beam diameter at the lens).
  • the onset of two-photon-induced polymerization was marked by the appearance of a ringed diffraction pattern in the far-field transmitted beam. Extensive cross-linking ultimately resulted in disruption of the far-field pattern and formation of a visible feature in the film.
  • the onset of polymerization occurred at pulse energies of 0.8 mJ, 0.6 mJ, 0.4 mJ, and 0.2 mJ for exposure times of 1 s, 2 s, 3 s, and 5 s, respectively.
  • the unpolymerized resin was removed by soaking the film in propylene glycol methylether acetate for 30 minutes. Free-standing columns of cross-linked polymer were present on the substrate in the irradiated regions.

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Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01136159A (ja) 1987-11-24 1989-05-29 Canon Inc 電子写真感光体
JPH01136160A (ja) 1987-11-24 1989-05-29 Canon Inc 電子写真感光体
US4931371A (en) 1987-11-24 1990-06-05 Canon Kabushiki Kaisha Electrophotographic photosensitive member
WO1998021521A1 (en) 1996-11-12 1998-05-22 California Institute Of Technology Two-photon or higher-order absorbing optical materials and methods of use
JPH118068A (ja) 1997-06-18 1999-01-12 Toyo Ink Mfg Co Ltd 有機エレクトロルミネッセンス素子材料およびそれを使用した有機エレクトロルミネッセンス素子
JPH1140359A (ja) 1997-07-22 1999-02-12 Toyo Ink Mfg Co Ltd 有機エレクトロルミネッセンス素子
JPH11102784A (ja) 1997-09-29 1999-04-13 Toyo Ink Mfg Co Ltd 有機エレクトロルミネッセンス素子材料およびそれを使用した有機エレクトロルミネッセンス素子
JPH11265786A (ja) 1998-03-17 1999-09-28 Japan Science & Technology Corp 分子発光デバイス
WO1999053242A1 (en) 1998-04-16 1999-10-21 California Institute Of Technology Two-photon or higher-order absorbing optical materials
US6086794A (en) 1997-03-26 2000-07-11 Mitsubishi Denki Kabushiki Kaisha Organic nonlinear optical material and nonlinear optical element using the same
US6267913B1 (en) 1996-11-12 2001-07-31 California Institute Of Technology Two-photon or higher-order absorbing optical materials and methods of use
US6852766B1 (en) * 2000-06-15 2005-02-08 3M Innovative Properties Company Multiphoton photosensitization system

Family Cites Families (80)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2807648A (en) 1955-09-16 1957-09-24 Stauffer Chemical Co Process for making sulfonium compounds
US4238840A (en) 1967-07-12 1980-12-09 Formigraphic Engine Corporation Method, medium and apparatus for producing three dimensional figure product
US3808006A (en) 1971-12-06 1974-04-30 Minnesota Mining & Mfg Photosensitive material containing a diaryliodium compound, a sensitizer and a color former
US3729313A (en) 1971-12-06 1973-04-24 Minnesota Mining & Mfg Novel photosensitive systems comprising diaryliodonium compounds and their use
US3741769A (en) 1972-10-24 1973-06-26 Minnesota Mining & Mfg Novel photosensitive polymerizable systems and their use
AU497960B2 (en) 1974-04-11 1979-01-25 Minnesota Mining And Manufacturing Company Photopolymerizable compositions
US4069056A (en) 1974-05-02 1978-01-17 General Electric Company Photopolymerizable composition containing group Va aromatic onium salts
GB1512982A (en) 1974-05-02 1978-06-01 Gen Electric Salts
US4058400A (en) 1974-05-02 1977-11-15 General Electric Company Cationically polymerizable compositions containing group VIa onium salts
US3981897A (en) 1975-05-02 1976-09-21 General Electric Company Method for making certain halonium salt photoinitiators
US4058401A (en) 1974-05-02 1977-11-15 General Electric Company Photocurable compositions containing group via aromatic onium salts
US4333165A (en) 1975-01-27 1982-06-01 Formigraphic Engine Corporation Three-dimensional pattern making methods
US4466080A (en) 1975-01-27 1984-08-14 Formigraphic Engine Corporation Three-dimensional patterned media
US4147552A (en) 1976-05-21 1979-04-03 Eastman Kodak Company Light-sensitive compositions with 3-substituted coumarin compounds as spectral sensitizers
US4090936A (en) 1976-10-28 1978-05-23 Minnesota Mining And Manufacturing Company Photohardenable compositions
US4151175A (en) 1976-12-09 1979-04-24 General Electric Company Method for making diarylhalonium salts
US4102687A (en) 1977-02-14 1978-07-25 General Electric Company UV Curable composition of a thermosetting condensation resin and Group VIa onium salt
US4471470A (en) 1977-12-01 1984-09-11 Formigraphic Engine Corporation Method and media for accessing data in three dimensions
US4162162A (en) 1978-05-08 1979-07-24 E. I. Du Pont De Nemours And Company Derivatives of aryl ketones and p-dialkyl-aminoarylaldehydes as visible sensitizers of photopolymerizable compositions
US4310469A (en) 1978-12-29 1982-01-12 General Electric Company Diaryliodonium salts
US4250053A (en) 1979-05-21 1981-02-10 Minnesota Mining And Manufacturing Company Sensitized aromatic iodonium or aromatic sulfonium salt photoinitiator systems
US4278751A (en) 1979-11-16 1981-07-14 Eastman Kodak Company Photopolymerization co-initiator compositions comprising amine-substituted ketocoumarins and certain acetic acid derivative activators
US4228861A (en) 1979-08-02 1980-10-21 Hart Thomas E Folding track removing implement
DE3008588A1 (de) * 1980-03-06 1981-09-17 Agfa-Gevaert Ag, 5090 Leverkusen Photographisches material fuer diffusionsverfahren
US4351893A (en) 1980-12-31 1982-09-28 E. I. Du Pont De Nemours And Company Derivatives of aryl ketones as visible sensitizers of photopolymerizable compositions
US4268667A (en) 1980-04-21 1981-05-19 E. I. Du Pont De Nemours And Company Derivatives of aryl ketones based on 9,10-dihydro-9,10-ethanoanthracene and p-dialkyl-aminoaryl aldehydes as visible sensitizers for photopolymerizable compositions
US4366228A (en) 1980-09-05 1982-12-28 Eastman Kodak Company Photopolymerizable compositions featuring novel co-initiators
CA1216998A (en) 1980-09-10 1987-01-20 Donald P. Specht Photopolymerization compositions comprising amine- substituted photosensitizers and n-heterocyclic compounds bearing an n-oxy substituent
JPS5815503A (ja) 1981-07-20 1983-01-28 Fuji Photo Film Co Ltd 光重合性組成物
US4450360A (en) 1982-03-12 1984-05-22 General Electric Company Alkylaryliodonium salts and method for making
US4399071A (en) 1982-03-12 1983-08-16 General Electric Company Method for making diaryliodonium salts
EP0127762B1 (en) 1983-05-02 1987-07-22 E.I. Du Pont De Nemours And Company Constrained n-alkylamino aryl ketones as sensitizers for photopolymer compositions
US5012001A (en) 1985-09-03 1991-04-30 General Electric Company Triaryl sulfonium photoinitiators
US4689289A (en) 1986-04-30 1987-08-25 General Electric Company Block polymer compositions
US4791045A (en) 1988-01-25 1988-12-13 Minnesota Mining And Manufacturing Company Photosensitizers and polymerizable compositions with mannich bases and iodonium salts
US4882201A (en) 1988-03-21 1989-11-21 General Electric Company Non-toxic aryl onium salts, UV curable coating compositions and food packaging use
US5047568A (en) 1988-11-18 1991-09-10 International Business Machines Corporation Sulfonium salts and use and preparation thereof
US5141969A (en) * 1988-11-21 1992-08-25 Eastman Kodak Company Onium salts and the use thereof as photoinitiators
US4921827A (en) 1988-11-23 1990-05-01 Minnesota Mining And Manufacturing Company Sensitized photoinitiator system for addition polymerization
US4992571A (en) 1989-10-31 1991-02-12 General Electric Company Method for making octyloxy substituted diphenyl iodonium hexafluoro metalloid salts
US5034613A (en) 1989-11-14 1991-07-23 Cornell Research Foundation, Inc. Two-photon laser microscopy
CA2034400A1 (en) 1990-04-30 1991-10-31 James Vincent Crivello Method for making triarylsulfonium hexafluorometal or metalloid salts
US5144051A (en) 1990-05-29 1992-09-01 Minnesota Mining And Manufacturing Company Branched alkoxyphenyl iodonium salt photoinitiators
US5079378A (en) 1990-07-27 1992-01-07 Polyset Corporation Preparation of diaryliodonium salt photoinitiators having long chain ester groups concatenated with aryl groups
US5089374A (en) * 1990-08-20 1992-02-18 Eastman Kodak Company Novel bis-onium salts and the use thereof as photoinitiators
US5086192A (en) 1990-12-14 1992-02-04 Minnesota Mining And Manufacturing Company Photopolymerizable compositions and photoinitiators therefor
US5102772A (en) 1991-07-10 1992-04-07 Ibm Photocurable epoxy composition with sulfonium salt photoinitiator
DE4142327A1 (de) 1991-12-20 1993-06-24 Wacker Chemie Gmbh Jodoniumsalze und verfahren zu deren herstellung
US5463084A (en) 1992-02-18 1995-10-31 Rensselaer Polytechnic Institute Photocurable silicone oxetanes
EP0571330B1 (de) * 1992-05-22 1999-04-07 Ciba SC Holding AG Hochauflösender I-Linien Photoresist mit höherer Empfindlichkeit
DE4219376A1 (de) 1992-06-12 1993-12-16 Wacker Chemie Gmbh Sulfoniumsalze und Verfahren zu deren Herstellung
US5274148A (en) 1992-08-10 1993-12-28 Isp Investments, Inc. Dialky alkoxy phenyl sulfonium salt cationic initiators
US5302757A (en) 1992-09-14 1994-04-12 Eastman Kodak Company Ultraviolet light sensitive onium salts
US5549962A (en) 1993-06-30 1996-08-27 Minnesota Mining And Manufacturing Company Precisely shaped particles and method of making the same
US5514728A (en) 1993-07-23 1996-05-07 Minnesota Mining And Manufacturing Company Catalysts and initiators for polymerization
EP0720520B1 (en) 1993-09-13 1999-07-28 Minnesota Mining And Manufacturing Company Abrasive article, method of manufacture of same, method of using same for finishing, and a production tool
WO1995030255A1 (en) 1994-05-02 1995-11-09 Minnesota Mining And Manufacturing Company Retroreflective polymer coated flexible fabric material and method of manufacture
ATE193311T1 (de) 1994-05-19 2000-06-15 Minnesota Mining & Mfg Polymergegenstand mit verbesserter hydrophiler eigenschaft und verfahren zu seiner herstellung
US5685754A (en) 1994-06-30 1997-11-11 Kimberly-Clark Corporation Method of generating a reactive species and polymer coating applications therefor
US5639413A (en) 1995-03-30 1997-06-17 Crivello; James Vincent Methods and compositions related to stereolithography
US6117612A (en) 1995-04-24 2000-09-12 Regents Of The University Of Michigan Stereolithography resin for rapid prototyping of ceramics and metals
US5591011A (en) 1995-09-18 1997-01-07 Carrier Corporation Multi-refrigerant compressor
GB9522683D0 (en) 1995-11-06 1996-01-10 Coates Brothers Plc Photoinitiator
US6232417B1 (en) 1996-03-07 2001-05-15 The B. F. Goodrich Company Photoresist compositions comprising polycyclic polymers with acid labile pendant groups
US5814355A (en) 1996-04-30 1998-09-29 Minnesota Mining And Manufacturing Company Mold for producing glittering cube-corner retroreflective sheeting
US6136212A (en) 1996-08-12 2000-10-24 The Regents Of The University Of Michigan Polymer-based micromachining for microfluidic devices
US6316519B1 (en) 1997-02-19 2001-11-13 E. I. Du Pont De Nemours And Company Molecular weight controlled polymers by photopolymerization
JP3773139B2 (ja) * 1997-03-31 2006-05-10 富士写真フイルム株式会社 ポジ型感光性組成物
WO1998050437A1 (en) 1997-05-05 1998-11-12 First Chemical Corporation Biradical photoinitiators
KR100551653B1 (ko) 1997-08-18 2006-05-25 제이에스알 가부시끼가이샤 감방사선성수지조성물
JP4204113B2 (ja) * 1997-12-04 2009-01-07 株式会社Adeka 新規な芳香族スルホニウム化合物、これからなる光酸発生剤およびこれを含む光重合性組成物、光造形用樹脂組成物ならびに光学的立体造形法
WO1999041296A1 (en) 1998-02-11 1999-08-19 Rensselaer Polytechnic Institute Photopolymerizable compositions containing cycloaliphatic epoxyalcohol monomers
EP1000090A1 (en) 1998-06-03 2000-05-17 Kimberly-Clark Worldwide, Inc. Novel photoinitiators and applications therefor
KR100279497B1 (ko) * 1998-07-16 2001-02-01 박찬구 술포늄 염의 제조방법
DE69930948T2 (de) 1998-09-28 2006-09-07 Kimberly-Clark Worldwide, Inc., Neenah Chelate mit chinoiden gruppen als photoinitiatoren
US6294698B1 (en) 1999-04-16 2001-09-25 Kimberly-Clark Worldwide, Inc. Photoinitiators and applications therefor
US6335144B1 (en) 1999-04-27 2002-01-01 Fuji Photo Film Co., Ltd. Photopolymerizable composition for short wavelength semiconductor laser exposure
JP2001147536A (ja) * 1999-11-22 2001-05-29 Fuji Photo Film Co Ltd ポジ型フォトレジスト組成物
US6346363B2 (en) 1999-12-06 2002-02-12 Fuji Photo Film Co., Ltd. Positive photoresist composition
JP2001255647A (ja) * 2000-03-13 2001-09-21 Daikin Ind Ltd エネルギー線照射によりカチオンまたは酸を発生するフルオロアルキルオニウム塩型のカチオンまたは酸発生剤

Patent Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01136159A (ja) 1987-11-24 1989-05-29 Canon Inc 電子写真感光体
JPH01136160A (ja) 1987-11-24 1989-05-29 Canon Inc 電子写真感光体
US4931371A (en) 1987-11-24 1990-06-05 Canon Kabushiki Kaisha Electrophotographic photosensitive member
WO1998021521A1 (en) 1996-11-12 1998-05-22 California Institute Of Technology Two-photon or higher-order absorbing optical materials and methods of use
US6267913B1 (en) 1996-11-12 2001-07-31 California Institute Of Technology Two-photon or higher-order absorbing optical materials and methods of use
US6086794A (en) 1997-03-26 2000-07-11 Mitsubishi Denki Kabushiki Kaisha Organic nonlinear optical material and nonlinear optical element using the same
JPH118068A (ja) 1997-06-18 1999-01-12 Toyo Ink Mfg Co Ltd 有機エレクトロルミネッセンス素子材料およびそれを使用した有機エレクトロルミネッセンス素子
JPH1140359A (ja) 1997-07-22 1999-02-12 Toyo Ink Mfg Co Ltd 有機エレクトロルミネッセンス素子
JPH11102784A (ja) 1997-09-29 1999-04-13 Toyo Ink Mfg Co Ltd 有機エレクトロルミネッセンス素子材料およびそれを使用した有機エレクトロルミネッセンス素子
JPH11265786A (ja) 1998-03-17 1999-09-28 Japan Science & Technology Corp 分子発光デバイス
US6529539B1 (en) * 1998-03-17 2003-03-04 Hitachi, Ltd. Molecular light emission device
WO1999053242A1 (en) 1998-04-16 1999-10-21 California Institute Of Technology Two-photon or higher-order absorbing optical materials
US6852766B1 (en) * 2000-06-15 2005-02-08 3M Innovative Properties Company Multiphoton photosensitization system

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Mariacristina Rumi, et al., "Structure-Property Relationships for Two-Photon Absorbing Chromophores: Bis-Donor Diphenylpolyene and Bis(styryl)benzene Derivatives", J. Am. Chem. Soc, vol. 122, 2000, 9500-9510.

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090323747A1 (en) * 2005-09-06 2009-12-31 Hajime Nakanotani Organic solid-state dye laser
US20100025226A1 (en) * 2006-05-19 2010-02-04 Joseph Callerame Configurations for Chlorine Dioxide Production
US20100207078A1 (en) * 2006-07-12 2010-08-19 Seth Marder Deprotection of functional groups by multi-photon induced electron transfer
US8192590B1 (en) * 2008-04-14 2012-06-05 University Of Central Florida Research Foundation, Inc. Microwave-assisted formation of sulfonium photoacid generators
US20110021653A1 (en) * 2009-07-22 2011-01-27 Lixin Zheng Hydrogel compatible two-photon initiation system
US20110245818A1 (en) * 2010-04-02 2011-10-06 Weinschenk Iii Joseph I Adjustable chromophore compounds and materials incorporating such compounds
CN102844683A (zh) * 2010-04-02 2012-12-26 诺瓦提斯公司 可调节发色团化合物及掺有该类化合物的材料
AU2011235140B2 (en) * 2010-04-02 2015-01-15 Alcon Inc. Adjustable chromophore compounds and materials incorporating such compounds
RU2563640C2 (ru) * 2010-04-02 2015-09-20 Новартис Аг Регулируемые хромофорные соединения и материалы, содержащие эти соединения
TWI583673B (zh) * 2010-04-02 2017-05-21 艾爾康股份有限公司 可調整之發色團化合物及併合該化合物之材料
US10029229B2 (en) 2010-04-02 2018-07-24 Novartis Ag Adjustable chromophore compounds and materials incorporating such compounds
CN102141731A (zh) * 2011-02-23 2011-08-03 同济大学 一类含二苯乙烯间位取代硫鎓盐类光生酸剂及其制备方法
CN103217868A (zh) * 2013-03-19 2013-07-24 同济大学 一类含双支化硫鎓盐光生酸剂、制备方法及其应用

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